{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,10]],"date-time":"2026-02-10T20:10:04Z","timestamp":1770754204814,"version":"3.50.0"},"reference-count":53,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2018,12,20]],"date-time":"2018-12-20T00:00:00Z","timestamp":1545264000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["IF\/01395\/2013\/CP1163\/CT005, CEECIND\/03708\/2017, UID\/QUI\/00100\/2013, LISBOA-01-0145-FEDER-029697, SFRH\/BPD\/119980\/2016"],"award-info":[{"award-number":["IF\/01395\/2013\/CP1163\/CT005, CEECIND\/03708\/2017, UID\/QUI\/00100\/2013, LISBOA-01-0145-FEDER-029697, SFRH\/BPD\/119980\/2016"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100018647","name":"RUDN University","doi-asserted-by":"publisher","award":["RUDN University Program 5-100"],"award-info":[{"award-number":["RUDN University Program 5-100"]}],"id":[{"id":"10.13039\/501100018647","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Innovation Team Project on University of Guangdong Province of P. R. China","award":["2017GKCXTD001"],"award-info":[{"award-number":["2017GKCXTD001"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(\u00b5-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(\u00b5-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) chloride as a metal source, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna) or 5-(3,4-dicarboxylphenyl)picolinic acid (H3dppa) as a principal building block, and 1,10-phenanthroline (phen) as a crystallization mediator. Compounds 1 and 2 were isolated as air-stable microcrystalline solids and fully characterized by elemental and thermogravimetric analyses, IR spectroscopy, powder and single-crystal X-ray diffraction. In the solid state, the structure of 1 discloses the linear interdigitated 1D coordination polymer chains with the 2C1 topology. The crystal structure of an ionic derivative 2 shows that the mono- and dicopper(II) units are extended into the intricate 1D hydrogen-bonded chains with the SP 1-periodic net (4,4)(0,2) topology. Thermal stability and catalytic properties of 1 and 2 were also investigated. In fact, both Cu derivatives act as efficient homogeneous catalysts (catalyst precursors) for the mild oxidation of cycloalkanes by hydrogen peroxide to give the corresponding alcohols and ketones; the substrate scope and the effects of type and amount of acid promoter as well as bond-, regio-, and stereo-selectivity features were investigated.<\/jats:p>","DOI":"10.3390\/molecules24010006","type":"journal-article","created":{"date-parts":[[2018,12,20]],"date-time":"2018-12-20T12:54:36Z","timestamp":1545310476000},"page":"6","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["New Copper(II) Coordination Compounds Assembled from Multifunctional Pyridine-Carboxylate Blocks: Synthesis, Structures, and Catalytic Activity in Cycloalkane Oxidation"],"prefix":"10.3390","volume":"24","author":[{"given":"Na","family":"Zhao","sequence":"first","affiliation":[{"name":"Foshan Research Center for Special Functional Building Materials and Their Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yu","family":"Li","sequence":"additional","affiliation":[{"name":"Foshan Research Center for Special Functional Building Materials and Their Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jinzhong","family":"Gu","sequence":"additional","affiliation":[{"name":"College of chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tiago A.","family":"Fernandes","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Marina V.","family":"Kirillova","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2052-5280","authenticated-orcid":false,"given":"Alexander M.","family":"Kirillov","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"},{"name":"Peoples\u2019 Friendship University of Russia (RUDN University), Research Institute of Chemistry, 6 Miklukho-Maklaya st., Moscow 117198, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2018,12,20]]},"reference":[{"key":"ref_1","unstructured":"Batten, S.R., Neville, S.M., and Turner, D.R. (2009). Coordination Polymers: Design, Analysis and Application, Royal Society of Chemistry."},{"key":"ref_2","unstructured":"MacGillivray, L.R., and Lukehart, C.M. (2014). Metal-Organic Framework Materials, John Wiley & Sons."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Kaskel, S. (2016). The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization, and Applications, 2 Volume Set, John Wiley & Sons.","DOI":"10.1002\/9783527693078"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1126","DOI":"10.1021\/cr200101d","article-title":"Luminescent functional metal-organic frameworks","volume":"112","author":"Cui","year":"2012","journal-title":"Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"76","DOI":"10.1016\/j.ccr.2013.10.023","article-title":"Lanthanide metal-organic frameworks for luminescent sensing and light-emitting applications","volume":"273\u2013274","author":"Cui","year":"2014","journal-title":"Coord. Chem. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1330","DOI":"10.1039\/b802352m","article-title":"Luminescent metal\u2013organic frameworks","volume":"38","author":"Allendorf","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"4680","DOI":"10.1021\/ja500191r","article-title":"Nanoporous cobalt(II) MOF exhibiting four magnetic ground states and changes in gas sorption upon post-synthetic modification","volume":"136","author":"Zeng","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1353","DOI":"10.1039\/b804757j","article-title":"Magnetic metal\u2013organic frameworks","volume":"38","author":"Kurmoo","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"12938","DOI":"10.1021\/acs.inorgchem.6b02376","article-title":"In situ generation of NiO nanoparticles in a magnetic metal-organic framework exhibiting three-dimensional magnetic ordering","volume":"55","author":"Meng","year":"2016","journal-title":"Inorg. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1477","DOI":"10.1039\/b802426j","article-title":"Selective gas adsorption and separation in metal-organic frameworks","volume":"38","author":"Li","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1294","DOI":"10.1039\/b802256a","article-title":"Hydrogen storage in metal-organic frameworks","volume":"38","author":"Murray","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"44","DOI":"10.1039\/B916295J","article-title":"Gas storage in porous metal\u2013organic frameworks for clean energy applications","volume":"46","author":"Ma","year":"2010","journal-title":"Chem. Commun."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3997","DOI":"10.1021\/acs.cgd.8b00344","article-title":"A usf zinc(II) metal-orgaic framework as a highly selective luminescence probe for acetylacetone detection and its postsynthetic cation exchage","volume":"18","author":"Zou","year":"2018","journal-title":"Cryst. Growth Des."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1670","DOI":"10.1039\/C7TC03863A","article-title":"A novel 2D coordination network built from hexacopper(I)-iodide clusters and cagelike aminophosphine blocks for reversible \u201cturn-on\u201d sensing of aniline","volume":"6","author":"Jaros","year":"2018","journal-title":"J. Mater. Chem. C"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"3272","DOI":"10.1039\/C7DT02966G","article-title":"Lanthanide-MOFs constructed from mixed dicarboxylate ligands as selective multi-responsive luminescent sensors","volume":"47","author":"Zhang","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"10649","DOI":"10.1002\/anie.201404470","article-title":"Enhanced separation of potassium ions by spontaneous K+-induced self-assembly of a novel metal\u2013organic framework and excess specific cation\u2013pi interactions","volume":"53","author":"Wu","year":"2014","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Garc\u00eda, H., and Naval\u00f3n, S. (2018). Metal-Organic Frameworks: Applications in Separations and Catalysis, John Wiley & Sons.","DOI":"10.1002\/9783527809097"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1450","DOI":"10.1039\/b807080f","article-title":"Metal-organic framework materials as catalysts","volume":"38","author":"Lee","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"361","DOI":"10.1021\/cs400959k","article-title":"Metal organic framework catalysis: Quo vadis?","volume":"4","author":"Gascon","year":"2014","journal-title":"ACS Catal."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2741","DOI":"10.1016\/j.ccr.2012.07.022","article-title":"Multicopper complexes and coordination polymers for mild oxidative functionalization of alkanes","volume":"256","author":"Kirillov","year":"2012","journal-title":"Coord. Chem. Rev."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"371","DOI":"10.1080\/00958972.2018.1439163","article-title":"Recent advances of one-dimensional coordination polymers as catalysts","volume":"71","author":"Loukopoulos","year":"2018","journal-title":"J. Coord. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4898","DOI":"10.1021\/acs.inorgchem.6b03084","article-title":"Cu(II) Coordination Polymers as Vehicles in the A3 Coupling","volume":"56","author":"Loukopoulos","year":"2017","journal-title":"Inorg. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"10776","DOI":"10.1002\/anie.201604313","article-title":"Flexible zirconium metal\u2013organic frameworks as bioinspired switchable catalysts","volume":"55","author":"Yuan","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"5169","DOI":"10.1021\/ic503061z","article-title":"Heterometallic Coordination Polymers Assembled from Trigonal Trinuclear Fe2Ni-Pivalate Blocks and Polypyridine Spacers: Topological Diversity, Sorption, and Catalytic Properties","volume":"54","author":"Sotnik","year":"2015","journal-title":"Inorg. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.ccr.2018.05.024","article-title":"Coordination polymers and metal-organic frameworks built up with poly (tetrazolate) ligands","volume":"372","author":"Pettinari","year":"2018","journal-title":"Coord. Chem. Rev."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.ccr.2015.08.005","article-title":"Coordination polymers and metal\u2013organic frameworks based on poly (pyrazole)-containing ligands","volume":"307","author":"Pettinari","year":"2016","journal-title":"Coord. Chem. Rev."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3312","DOI":"10.1021\/cg300442b","article-title":"pH and auxiliary ligand influence on the structural variations of 5(2\u2032-carboxylphenyl) nicotate coordination polymers","volume":"12","author":"Gu","year":"2012","journal-title":"Cryst. Growth Des."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"4658","DOI":"10.1021\/acs.cgd.6b00735","article-title":"Structurally distinct metal-organic and H-bonded networks derived from 5-(6-carboxypyridin-3-yl)isophthalic acid: Coordination and template effect of 4,4\u2032-bipyridine","volume":"16","author":"Gu","year":"2016","journal-title":"Cryst. Growth Des."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"5164","DOI":"10.1039\/C6CE00853D","article-title":"Anion- and temperature-dependent assembly, crystal structures and luminescence properties of six new Cd(II) coordination polymers based on 2,3,5,6-tetrakis(2-pyridyl)pyrazine","volume":"18","author":"Wan","year":"2016","journal-title":"CrystEngComm"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"3683","DOI":"10.1021\/acs.cgd.8b00498","article-title":"Luminescent coordination polymers of naphthalene based diamide with rigid and flexible dicarboxylates: Sensing of nitro explosives, Fe(III) ion, and dyes","volume":"18","author":"Das","year":"2018","journal-title":"Cryst. Growth Des."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"906","DOI":"10.1039\/C7CE02009K","article-title":"Bringing 5-(3,4-dicarboxylphenyl) picolinic acid to crystal engineering research: Hydrothermal assembly, structural features, and photocatalytic activity of Mn, Ni, Cu, and Zn coordination polymers","volume":"20","author":"Gu","year":"2018","journal-title":"CrystEngComm"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"7431","DOI":"10.1039\/C8DT01299G","article-title":"A new series of Co, Ni, Zn, and Cd metal-organic architectures driven by an unsymmetrical biphenyl-tricarboxylic acid: Hydrothermal assembly, structural features and properties","volume":"47","author":"Gu","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_33","doi-asserted-by":"crossref","unstructured":"Gu, J.-Z., Wen, M., Liang, X., Shi, Z.-F., Kirillova, M.V., and Kirillov, A.M. (2018). Multifunctional Aromatic Carboxylic Acids as Versatile Building Blocks for Hydrothermal Design of Coordination Polymers. Crystals, 8.","DOI":"10.3390\/cryst8020083"},{"key":"ref_34","unstructured":"Karlin, K.D., and Tyeklar, Z. (2012). Bioinorganic Chemistry of Copper, Springer."},{"key":"ref_35","doi-asserted-by":"crossref","unstructured":"Karlin, K.D., Itoh, S., and Rokita, S. (2011). Copper-Oxygen Chemistry, Wiley.","DOI":"10.1002\/9781118094365"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"125","DOI":"10.1021\/acs.inorgchem.5b01983","article-title":"Copper(II) coordination polymers self-assembled from aminoalcohols and pyromellitic acid: Highly active precatalysts for the mild water-promoted oxidation of alkanes","volume":"55","author":"Fernandes","year":"2016","journal-title":"Inorg. Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"525","DOI":"10.1039\/C4QI00220B","article-title":"New tricopper(II) cores self-assembled from aminoalcohol biobuffers and homophthalic acid: Synthesis, structural and topological features, magnetic properties and mild catalytic oxidation of cyclic and linear C5\u2013C8 alkanes","volume":"2","author":"Dias","year":"2015","journal-title":"Inorg. Chem. Front."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"5204","DOI":"10.1021\/acs.inorgchem.5b00048","article-title":"New tetracopper(II) cubane cores driven by a diamino alcohol: Self-assembly synthesis, structural and topological features, and magnetic and catalytic oxidation properties","volume":"54","author":"Dias","year":"2015","journal-title":"Inorg. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2353","DOI":"10.1039\/b900853e","article-title":"Alkanes to carboxylic acids in aqueous medium: Metal-free and metal-promoted highly efficient and mild conversions","volume":"17","author":"Kirillova","year":"2009","journal-title":"Chem. Commun."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"10141","DOI":"10.1039\/C5DT00460H","article-title":"Double-step CO2 sorption and guest-induced single-crystal-to-single-crystal transformation in a flexible porous framework","volume":"44","author":"Wu","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"9943","DOI":"10.1039\/C7TC02430D","article-title":"A highly sensitive turn-on ratiometric luminescent probe based on postsynthetic modification of Tb3+@Cu-MOF for H2S detection","volume":"5","author":"Zheng","year":"2017","journal-title":"J. Mater. Chem. C"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"10908","DOI":"10.1039\/C7DT01742A","article-title":"Hydrothermal assembly, structures, topologies, luminescence, and magnetism of a novel series of coordination polymers driven by a trifunctional nicotinic acid building block","volume":"46","author":"Gu","year":"2017","journal-title":"Dalton Trans."},{"key":"ref_43","unstructured":"Ellis, W.B. (2008). Ullmann\u2019s Encyclopedia of Industrial Chemistry, Wiley-VCH. [6th ed.]."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/S0926-860X(01)00472-0","article-title":"Cyclohexane Oxidation Continues to be a Challenge","volume":"211","author":"Schuchardt","year":"2001","journal-title":"Appl. Catal. A Gen."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"732","DOI":"10.1016\/j.ccr.2012.09.012","article-title":"Pyrazinecarboxylic acid and analogs: Highly efficient co-catalysts in themetal-complex-catalyzed oxidation of organic compounds","volume":"257","author":"Kirillov","year":"2013","journal-title":"Coord. Chem. Rev."},{"key":"ref_46","doi-asserted-by":"crossref","unstructured":"Shul\u2019pin, G.B. (2016). New trends in oxidative functionalization of carbon\u2013hydrogen bonds: A review. Catalysts, 6.","DOI":"10.3390\/catal6040050"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"4217","DOI":"10.1039\/c004223d","article-title":"Selectivity enhancement in functionalization of C\u2013H bonds: A review","volume":"8","year":"2010","journal-title":"Org. Biomol. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"12794","DOI":"10.1039\/c3dt51004b","article-title":"C\u2013H functionalization: Thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst\u2019s activity and selectivity","volume":"42","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_49","first-page":"3","article-title":"Crystal Structure Refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Cryst."},{"key":"ref_50","first-page":"4","article-title":"Multipurpose crystallochemical analysis with the program package TOPOS","volume":"7","author":"Blatov","year":"2006","journal-title":"IUCr CompComm Newsl."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"3576","DOI":"10.1021\/cg500498k","article-title":"Applied topological analysis of crystal structures with the program package topospro","volume":"14","author":"Blatov","year":"2014","journal-title":"Cryst. Growth Des."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"39","DOI":"10.1016\/S1381-1169(02)00196-6","article-title":"Metal-catalyzed hydrocarbon oxygenations in solutions: The dramatic role of additives: A review","volume":"189","year":"2002","journal-title":"J. Mol. Catal. A Chem."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"95","DOI":"10.2174\/157019309788167738","article-title":"Hydrocarbon oxygenations with peroxides catalyzed by metal compounds","volume":"6","year":"2009","journal-title":"Mini-Rev. Org. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/1\/6\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T15:35:11Z","timestamp":1760196911000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/1\/6"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,12,20]]},"references-count":53,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2019,1]]}},"alternative-id":["molecules24010006"],"URL":"https:\/\/doi.org\/10.3390\/molecules24010006","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,12,20]]}}}